Nanoscale multilayers offer outstanding possibilities in the technology of various nanoscale photonic or electronic devices. A widespread way to probe nanometric layers is to employ optical reflection methods. A purpose of this paper, first, is to model analytically the reflection characteristics in the long-wavelength limit for an N-layer system of nanoscale anisotropic multilayers on isotropic transparent materials and to show by numerical calculations on the basis of exact electromagnetic theory what is the level of accuracy of this approximation. A second aim is to investigate new possibilities for determining the parameters of anisotropic nanofilms. In this paper the second-order analytical formulas for the reflection (transmission) characteristics of an N-layer system of anisotropic nanofilms on a nonabsorbing substrate are derived. The approximate results are supported by computer-aided analysis made on the basis of general wave propagation theory for anisotropic layered media. The most useful feature of obtained analytical expressions is that they are simply invertible, allowing a direct calculation of the parameters of nanoscale layers. It must be emphasized that this technique allows overcome the correlation between thickness and dielectric response inherent in some reflection methods.